Producing vat dyestuffs



Patented Feb. 23, 1932 UNITED STATES,

PATENT OFFICE MAX ALBERT KUNZ, OF MANNHEIM, AND KARL KdBE-RLE, O1 LUDWIGSHAFEN -ON-THE- BHINE, GERMANY, ASSIGNORS TO GENERAL ANILINE- WORKS, INC-,0! NEW YORK,

N. Y., A. CORPORATION OF DELAWARE rnonucme var nvns'rurrs No Drawing. Application flled J'anuary 11, 1928, Serial No. 246,078, and in Germany January 14, 1927.

pended claims, is meant to comprise msbenzdianthrones, ms-naphthodianthrones, allo-ms-naphthodianthrones, ms-anthradianthrones, dibenzanthrones and isodibenzanthrones. Accordingly the said anthrone radical combinations are compounds containin g one of the r'ollowing ring systems:

The anthrone radical combinations maybe substituted by any negative substituents such as halogen atoms or nitro groups and the like. As nitrogenous compounds containing at least one reactive hydrogen atom on the nitrogen atom which may be condensed with the said anthrone radical combinations, aminoanthraquinones and their derivatives are particularly suitable, since the introduction of the anthraquinonylamine radicle substantially dyestuffs. The condensation mayalso be effected with ammonia, carbazol, isatine, toluenesulphamide and other nitrogenous compounds of the kind specified. The reaction is preferably carried out in solvents or suspension agents of high boiling point, such as nitrobenzene, naphthalene, andlthelike, and in the presence of catalysts such as copper or copper compounds or of acid-fixing agents,

faciliates the vatting of the new or both. In most cases it proceeds quantitatively.

Depending on the a Working conditions adopted, the halogen atoms in those ofthe said anthrone radical combinations, which contain several halogen atoms, may be wholly or partially replaced by the nitrogenous radicle, and the resulting products give exceedingly fast brown-yellow or grey to blue-black or violet-black'dyeings on cotton from brown or blue to brown-violet or bluish-violet vats. Analogous dyestuffs are also obtained by condensing intermediate products containing at least one negative substituent, which intermediate products on further condensation yield the said anthrone radical combinations, with a nitrogenous compound containing at? least one reactive hydrogen atom on the nitrogen atom and then further condensing the reaction products to dyestuffs containing one of the above described ring systems. As'intermediate products of the said kind may be mentioned dianthraquinonyls, dibenzan-' thronyls, or 2.2 dimethyl ms benzdian thrones containing a negative substituent. Those of the said dyestuffs which contain more than one linking ring between the anthrone radicals may also be produced when further condensing the dyestuffs obtained from anthrone radical combinations containing a smaller number of linking rings such as those derived from ms-naphthodianthrones allo-ms-naphthodianthrones or vmsanthrac'lianthrones in the manner described in our copending application for patent Ser. No.,199,420. Thus, for instance, a dyestuif similar to tri-aminoanthraquinonyl-msnaphthodianthrone obtainable from tribromms-naphthodianthrone, and an amino-anthraquinone can be obtained by condensing the reaction product between tribrom-ms-benzdianthrone and an amino-anthraquinone with aluminium chlorid. Instead of starting from tribrom-ms-benz-dianthrone also tribromanthraquinonyl may be used as initial material which after condensation with an amino- 1 anthraquinone may be first condensed to tri- Lat.

amino-anthraquinonylms benz dianthrones and the latter then condensed by means for instance of aluminium chlorid to tri-aminoanthraquinonyl-ms-naphthodianthrone.

For the purposes of the present invention it is not necessary that the anthrone radical v combinations or the intermediate products leading to the formation of the said combinations are substituted by a negative substituent and the other compound to be condensed i therewith contain a nitrogen atomto which at least one reactive hydrogenatom is attached, but analogous dyestuffs are obtained when condensing anthrone radical combinations or the said intermediate products containing anitrogen atom to which at least one reactive hydrogen atom is attached, with another compound which is substituted by at least one negative substituent. v

The following examples willfurther'illustratethe nature of this invention but the, in

vention is not limited to these examples. The

7 parts of tetrabrom-ms-benzdianthrone (see Berichte der Deutschen Chemischen Gesellschaft, vol. 43, p. 17 34:) are stirred and boiled for 15 hours in 100 parts of nitrobenzene, with 5 parts of sodium acetate, 8.8 parts of a-aminoanthraquinone and 1.5 parts of basic copper carbonate. After cooling, the residue is filtered and boiled with water, leaving 'behind'the dyestulf' corresponding 'to" the formula: f c

in the form ofia violet powder, free from halogen which gives aviolet solution in concentrated sulfuric acid and furnishes a brownishfviolet vat with an alkaline hydro sulfite solution. In contrast, to the very weak orange shades obtained with tetrabrom-msbenzdianthrone, the dark violet dyeings on cotton are very fast tolight. Eadmple? 31 parts of tribrom-m's-benzdianthrone obtainable according to Example 2 of the copending application Ser. No. 199,421, are stirred and boiled for about 12 hours with 40 "parts of a-aminoanthraquinone in 300 parts of nitrobenzene, after the addition of 20'p'artsof sodium acetate. After'cooling, the same treatment is applied as Example 1. The-resulting dy'estuf't' correspond-ingto the formula:

is a violet powder giving a violet solution in concentrated sulfuric acid, a brownish-violet vat,'and strong violet dyeings' on cotton.

. I .L'Ea P QY 6.2 parts oftribrom-ms benzdianthrone whole gently are dissolved in 100 parts of nitrobenzene, 7.5 parts of l-amino-4-methoxy-anthraquinone, 5 parts of sodium acetate and 0.5 part of copper carbonate being added, and the boiled, while stirring, for about 2-1 hours. a After cooling and filtering, the residue is boiled with water and dried, leaving the dyestuif corresponding to the formula:

in the form of a blue-black powder which is free from halogen, dissolves to a blue-green solution in concentrated sulfuric acid, and gives greyish-blue dyeings on cotton from a brownish-violet vat. i

E xamplc J;

A solution of 4.85 parts of trichlor-1nsbenzdianthrone obtainable according to Example 3 of the copending application Ser.

No. 199,421, in 100 parts of nitrobenzene, is

Example 5 6.2 parts of tribrom-msbenzdianthrone, 6.6 parts of B-aminoanthraquinone, 5 parts of sodium acetate and 0.5 part of copper carbonate are stirred and boiled in 100 parts of nitrobenzene for about 12 hours, the reaction product being boiled with water, after cooling and filtration. It gives a blue solution in concentrated sulfuric acid, a brownish-red vat, and very fast copper-red dyeings on cotton.

Example 6 5 l7 parts of 4.4-dichlor-22-dimethyl-msbenzdianthrone obtainable by reducing 4.4- dichlor- .2 -din1ethyl-1.1 dianthraquinonyl in acid solution, in 1000 parts of nitrobenzene are stirred and boiled for about 12 hours copper carbonate and 46 parts of a-aminoanthraquinone, and treated in the usual manner. The resulting dycstufi is obtained in r the form of a violet powder which dissolves to a greenislryellow solution in concentrated with 25 parts of sodium acetate, 1.5 parts of.

sulfuric acid and gives violet dyeing s on cotton fromabrown vat.

Example '7 62 parts of tribrom-ms-naphthodianthrone, 7

obtainable from tribrom-ms-benzdianthrone by heating with aluminium chlorid, are stirred and boiled for about 6 hours in 2000 parts of nitrobenzene with parts of a-aminoanthraquinone, 50 parts of sodium acetate and 5 parts of copper carbonate. The deposit is filtered by suction, boiled with water and dried. V The resulting violet powder, which still contains halogen, gives a brownish red solution in concentrated sulfuric acid, a brown vat, and extremely fast reddishviolet dyeings on cotton. a

A dyestuif of almost equal properties is obtained when condensing the dyestufl' obtained according to Example 2 with aluminium chlorid.

Example 8 f 18 parts of the tetrabrom-Ins-naphthodianthrone obtainable by treating tetrabronims-benzdianthrone with aluminium chlorid,

are stirred and boiled for about 12 hours with 20 parts of waminoanthraquinone and 10 parts of sodium acetate in 350 parts of nitrobenzene, and treated as specifiedin Example 7. The resulting dyestufl, a violet powder, gives very fast red-violet dyelngs on cotton from a brown vat.

Example .9

E xample 10 50 parts of dichlor-ms-naphthodianthrone, obtainable by chlorinating ms-naphthodianthrone, are stirred and boiled for about 8 hours in 1000 parts of nitroben zene with 45 parts of a-aminoanthraquinone, 25 parts of sodium acetate and 2.5 parts of copper car,- bonate, and treated in the usual manner. The dyestuff is obtained in the form of a vio let powder, which is free from halogen, dissolves to a violet solution in concentrated sulfuric acid, and furnishes a brownish-red vat from which claret dyeings are obtained on cotton. i

Example 11 A suspension of 30parts of brorn-2.2'-dimethyl-ms-naphthodianthrone, obtainable by black crude product dissolves to a violet solu-' tion in concentrated sulfuric acid, and gives powerful olive green dyeings on cotton from a brown vat.

The product obtainable fromtetrabromms-naphthodianthrone and 1-amino-4-niethoxyanthraquinone in a similar manner, dissolves to a blue solution in concentrated sul-' furic acid, and gives dark blue dyeings from a brown vat.

Example 12 7.2 parts of tetrabrom-allo-ms-naphthodianthrone obtainable according to Example 19 of the copending application Ser. No. 199,420, are stirred and boiled for about 6 hours in parts of nitrobenzene with 5 parts of sodium acetate, 0.3 part of copper carbonate and 44 parts of oc-lll'llIlOIlilDthIlQlllIlOIlG. After cooling. thedeposit is'filtered by suction, boiled with water and dried. The resulting dark blue powder, which contains halogen, gives a green solution with concentrated sulfuric acid, brownish-violet vats and very fast dark navy blue dyeings on cotton.

Example 13 A solution of 30 parts of dibrom-allo-msnaphthodianthrone obtainable according to Example 17 of the copending application Ser. N0. 199,420, and 30 parts of a-aminoanthraquinone in 250 parts of nitrobenzene is treated with 20 parts of sodium acetate and boiled, while stirring, for about 12 hours, the deposit being filtered by suction after cooling and treated as in Example 12. The resulting dark blue powder gives a green solution in concentrated sulfuric acid, and dark navy blue dyeings on cotton from a brownish-violet vat.

Example 14 4.7 5 parts of dichlor-allo-msrnaphthodianthrone, the'dyestufi obtainable according to Example 15 of the copen ding application Ser. No. 199,420, -5 parts of 1-amino-4- methoxyanthraquinone, 3 parts of sodium acetate and 0.3 part of copper carbonate are suspended in 50 parts of nitrobenzene, and boiled while stirring, for about 12 hours, the product being then filtered by suction in the cold and treated in the usual manner. The resulting dyestuff gives a green solution in concentrated sulfuric acid, violet vats and naphthodianthrone in parts of nitrobenzene is stirred and boiled during 18 hours with the addition of 5 parts of B-amino:

anthraquinone,'5 parts of sodium acetate and 0.5 part of copper carbonate. After cooling, the residue is filtered by suction and boiled With water. The brown reaction product gives a green solution in concentrated sulfuric acid, and copper-red-dyeings on cotton from a deep violet vat.

I Ewample 16' 47 parts of dichlor-allo-rns-naphthodianthrone are stirred and boiledduring '12 hours in 500 parts of nitrobenzene with 3 parts of sodium acetate, 2.5 parts of copper carbonate and 5 parts of 'p-toluene-sulfami-de. After cooling and filtering, the deep violet residue is dissolvedin concentrated sulfuric acid at 80 to 100 centigrade and precipitated therefrom by dilution. The resulting di-aminoallo-ms-naphthodianthrone is a violet powder, which gives a green solution with concentrated sulfuricaci'd, andviolet dyeings, fast to chlorine on cotton from a violet vat.

The same dyestuif is obtained when bringing dichlor-allo-ms-naphthodianthrone to reaction with ammonia. I 'The di-amino-allo-ms-naphthodianthrone can of course be further condensed with compounds containing a negative substituent such as, for instance, 1-chlor-4-methoxy-anthraqui-' none and a dyestufl' is obtained with similar coloring properties as the dyestuff obtained according to Example 14.

throne are boiled while stirring, for 15 hours in 47 5 parts of nitrobenzene with 25 parts of sodium acetate, 0.5 part of copper'carbonate and 49 parts of 1.5 diamino-anthraquinone. The reaction product is worked up as described in Example 1; it gives a green solution in concentrated sulfuric acid and dyes cotton violet-black shades of excellent fastness especially to chlorine from a brownviolet vat.

' Ewample 18 36 parts of tetrabrom-allo-ms-napththoidianthrone are stirred and boiled-during 6' hours in 720 parts of nitrobenzene with 48 parts of 1-amino-2-methyl-anthraquinone, after the addition of 25 parts of sodium acetate and 2.5 parts ofcopper carbonate, and are then treated in the usual manner. The resulting dyestuff, a dark blue powder, gives violet vats and dark blue dyeings on cotton.

Ewample 1.9

56 parts of dibrom-ms-anthradianthrone, obtainable according to Example 25 of the copending application Ser. No. 199,420, are stirred and boiledduring 12 hours with 46 parts of waminoanthraquinone and 25 parts of sodium acetate in 1000 parts of nitrobenzene. After cooling and filtering by suction the residue is boiled with water, again filtered and dried. The resulting brownish-violet dyestuff gives a blue solution with concentrated sulfuric acid and very fast deep violet dyeings on cotton from a brownish-violet vat.

The same dyestuif is also obtained when further condensing the dyestuff produced according to Example 13 with the aid of oxidizing agents or aluminum chlorid.

E wample 20 lngs on cotton from a brown vat.

Ewample 21 28 parts of dibrom-ms-anthradianthrone, are stirred and boiled for 12 hours with 25 parts of 1-amino-4-methoxy-anthraquinone, 15 parts of sodium acetate and 1 part of copper oxid, in 250 parts of nitrobenzene. Treatment in the usual manner leaves the resulting dyestuif in the form of a bluish-violet powder, which gives a blue solution in concentrated sulfuric acid and very fast greyish-blue dyeings on cotton from a brown vat.

Example 22 36 parts oftetrabrom-lns-anthradianthrone, obtainable by heating tetrabrom-allo-msnaphthodianthrone with aluminium chlorid, are stirred and boiled for 20 hours in 4.00 parts of nitrobenzene with 50 parts of ptoluene-sulfamide, 2 parts of copper carbonate and 25 parts of sodium acetate, and after cooling are treated as described in Example 19. The residual deep violet powder, is dissolved in concentrated sulfuric acid at 90 to 100 centigrade and precipitated from the solution by dilution, whereupon the diamino-ms-anthradianthrone is obtained as a violet paste. It gives violet dyeings on cotton from a brownish-violet vat.

An analogous product is obtained when treating ms-anthradianthrone with nitratof copper carbonate,

with 1 soquinone; the reaction product is filtered ofi' by "suction, while hot, and is then boiled with waterand dilute acid for removing inorganic constituents, and dried after filtration. The black powderobtained gives a blue solution with concentrated sulfuric acid and grey to blue-black dyeings of excellent fastness oncotton from a blue vat.

Emample 24 11 parts of dichlor-dibenzanthrone obtainable by chlorinatingdibenzanthrone in chlor-sulfonic acid in the presence of sulfur are suspended in 100 parts of nitrobenzene; 5 parts of sodium acetate, 1.5 parts .of copper carbonate and 5 parts of 1.4-amino-methoxyanthraquinone are added and the mixture is boiled for 20 hours while stirring. The reactionproduct is filtered off by suction while hotand worked up as described in Example 23. The black powder so obtained dyes cotton from a green-blue vat blue-grey to blueblack shades of excellent fastness and dissolves to a blue solution in concentrated sulfuric acid. a

Example 25 p 62parts of dibrom-isodibenzanthrone obtainable by brominating isodibenzanthrone in nitrobenzene are boiled for 15 hours while stirring in a mixture of 1000parts of nitrobenzene,'30 parts of sodium acetate,'2 parts 5 parts of cupric oxid and 50' parts of 1.4aamino-methoxy-anthraquinone. The reaction product is filtered on by suction whilehot and worked up as described in Example 23. The grey-black powder obtained dyes cotton violet-grey shades of excellent. fastness from a greenblue vat and 'givesblue solutionsin concentrated sulfuric acid.

What we claim is:

1. As new articles of manufacture msbenzdianthrones to which at least one other organic radical is attached by nitrogen linkage. a l

2. As new articles of manufacture msbenzdianthrones to which at least one anthraquinonyl radical is attached by, nitrogen linkage. p y

3. As new articles of manufacture msbenzdianthrones to which at least one anthraquinonyl radical is attached in the a-PO- sition by nitrogen linkage.

of: manufacture the ehAsv anew article.

dyestuff correspondingto the formula:

forming a violet powder, free from halogen giving aviolet solution in concentrated sulfuric acid and dyeing cotton dark violet shades very fast to light'from a brownish violet vat. v

5. The process of producing new vat dye stufls which comprises condensing a msbenzdianthrone witha compound, one of the said components containing atleast' one halogen atom, the other at least one reactive hydrogen atom attached to a nitrogen atom in a diluting medium of high boiling point in the presence of a condensing catalyst containing copper and an acid-fixing agent.

6; The process of producing new vat dyestufis which comprises condensing a halogenated ms-benzdianthrone with a nitrogenous compound containing at least one reactive hydrogen atom on a nitrogen atom in a diluting medium of high-boiling point in the presence ofa condensing'catalyst containing copper and an acid-fixing agent.

7. The process of producing new vat dyestufi's which comprises condensing a halogenated ms-benzadlanthrone with a nitrogenous compound containing at least-one reactive hydrogen atom on a nitrogen atom in a diluting medium of high boiling point in the presence of acondensing catalyst containing copper and an acid-fixing agent.

8. The dyestuffs which comprises condensing a halogenated ms-benzdianthrone with a nitrogenous com-pound containing at least one reactive hydrogen atom on a nitrogen atom in a diluting medium. of high boiling point in the presence of a condensing catalyst containing copper and an acid-fixing agent.

The process of producing new vat dyestufi's which comprises condensing a'halogenated ms-benzdianthrone with a enous compound containing at least one reactive hydrogen atom on a nitrogen atom in a diluting medium of high boiling point in the presence of a condensing catalyst containing copper and an acid-fixing agent.

10. The process of producing new vat dyestuffs whichcomprises condensing a halogenated ms-benzdianthrone with anitrogenous compound containing at least one reactive hydrogen atom on a nitrogen atom in a div 11. The process of producing new vat dyeprocess of producing new vat nitrogluting medium of high; boiling point in the presence, of a condensingcatalyst containing.

copper and a salt of an alkali "metal and: a

wea acid.

stufi's which comprises condensing a halogenated ms-benzdianthrone with an aminoanthraquinone in a diluting medium of" high boiling point in the presence of a condensing catalyst containing copper and an acid-fixing agent. 1

V 12. The process of producing new vat dyestuffs which comprises condensing a halogenated ms-benzdianthrone with an a-aminoanthraquinone in a diluting medium of high boiling point in the presence of a condensing catalyst containing copper and an acid-fixing agent. i V

13. The process of producing a new vat dyestufi which comprisescondensing about 135 one molecular proportion of tetrabrommsbenzdianthrone with about 4 molecular proportions of a-amino-anthraquinone in a di luting medium of high boilingpoint in the presence of a condensing catalyst containing 99 copper and an acid-fixing agent.

Intestimony whereof we have hereunto set our hands.

MAX ALl3ERT KUNZ. KARL KOBERLE; 

